EP3904421A1 - Polyol de polyéther modifié et son utilisation dans des matériaux en mousse de polyuréthane - Google Patents

Polyol de polyéther modifié et son utilisation dans des matériaux en mousse de polyuréthane Download PDF

Info

Publication number
EP3904421A1
EP3904421A1 EP18944686.7A EP18944686A EP3904421A1 EP 3904421 A1 EP3904421 A1 EP 3904421A1 EP 18944686 A EP18944686 A EP 18944686A EP 3904421 A1 EP3904421 A1 EP 3904421A1
Authority
EP
European Patent Office
Prior art keywords
polyether polyol
oxidized
catalyst
group
tertiary amines
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18944686.7A
Other languages
German (de)
English (en)
Other versions
EP3904421A4 (fr
Inventor
Fuguo LI
Yang Liu
Changxun JU
Naihua JIANG
Bin Liu
Chengqun QIN
Lunpeng Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Publication of EP3904421A1 publication Critical patent/EP3904421A1/fr
Publication of EP3904421A4 publication Critical patent/EP3904421A4/fr
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/636—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the presence of a dispersion-stabiliser
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/10—Water or water-releasing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

  • the present disclosure relates to a synthesis of a modified polyether polyol and the use thereof and, in particular, to a synthesis of a modified polyether polyol with multiple active sites and the use thereof as a dispersion stabilizer in a synthesis of a copolymer polyol.
  • Polyurethane foam is prepared by reacting a polyisocyanate with a polyol in the presence of a foaming agent.
  • Various modified polyol products have been developed by those skilled in the art in order to improve a bearing property and other properties.
  • Common types are dispersions of polymer particles in polyols, such as vinyl polymer particle polyols (styrene-acrylonitrile dispersions), polyurea particle dispersions (PHD polyols), and polyisocyanate addition polymers (PIPA polyols and polyurethane-polyurea particle dispersions).
  • a polyether polyol starting from sorbitol or pentaerythritol is reacted with maleic anhydride in the presence of a catalyst to perform a ring-opening reaction, followed by a reaction with alkylene oxide such as ethylene oxide or propylene oxide. Unsaturation is introduced by maleic anhydride.
  • the process is concise, the reaction is complete, and the device is low in cost.
  • a polymeric polyol synthesized with a stabilizer prepared with maleic anhydride has high viscosity.
  • EP02253584 has disclosed a stabilizer prepared by reacting phthalic anhydride with glycidyl methacrylate in the presence of a catalyst.
  • the synthesis takes a long time and uses an organotin catalyst which remains in the copolymer polyol and affects a subsequent reaction of a hydroxyl compound with an isocyanate, causing a foam product to fall back, irregular foam pores, and pore collapse in an extreme formulation.
  • the present disclosure provides a method for preparing a modified polyether polyol.
  • the modified polyether polyol prepared by the method has more active sites, and has the characteristics of good dispersion stability, good filterability and low viscosity when served as a dispersion stabilizer in synthesis of a copolymer polyol.
  • One aspect of the present disclosure provides a method for preparing a modified polyether polyol, comprising the following steps:
  • a molar ratio of the compound A to the polyether polyol is 0.5-1.5: 1, preferably 0.9-1: 1; and a molar ratio of the compound A to the epoxy compound is 0.2-4: 1, preferably 0.5-1.5: 1.
  • the reaction temperature in step (1), is 80-160 °C, preferably 120-140 °C; and in step (2), the reaction temperature is 60-150 °C, preferably 80-130 °C.
  • the compound A in step (1), may be reacted with the polyether polyol in the presence or absence of a catalyst.
  • the reaction is performed in the presence of a catalyst, where the catalyst is used in an amount of preferably 0.1 ⁇ to 3 ⁇ , for example 0. 1 ⁇ of the mass of the polyether polyol.
  • the catalyst used may be one or a combination of two or more of carbonates, bicarbonates, and hydroxides of alkali metals or alkaline earth metals, preferably one or a combination of two or more of hydroxides of alkali metals, for example, but not limited to, one or more of sodium hydroxide, potassium hydroxide, and the like.
  • the hydroxides of alkali metals may be used alone or in solution, where a solvent is preferably one or a combination of two or more of water, alcohols, ethers, amines, and ammonia, and is more preferably used in the form of an aqueous solution.
  • the epoxy compound containing a polymerizable double bond is any 1,2-epoxide containing an olefinic double bond, for example, one or a combination of two or more selected from glycidyl methacrylate, glycidyl acrylate, and derivatives thereof, preferably one or a combination of two or more of allyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate, more preferably glycidyl methacrylate.
  • the catalyst used in step (2) preferably adopts a composite catalyst comprising a catalyst A and a catalyst B, wherein the catalyst A is an oxidized tertiary amine compound, for example, one or a combination of two or more of oxidized aryl tertiary amines, oxidized alkyl tertiary amines, oxidized cycloalkyl tertiary amines, oxidized acyl tertiary amines, and oxidized hydroxyl-substituted tertiary amines.
  • the catalyst A is an oxidized tertiary amine compound, for example, one or a combination of two or more of oxidized aryl tertiary amines, oxidized alkyl tertiary amines, oxidized cycloalkyl tertiary amines, oxidized acyl tertiary amines, and oxidized hydroxyl-substituted tert
  • the oxidized aryl tertiary amines are, for example, oxidized dimethylanilines;
  • the oxidized alkyl tertiary amines are, for example, one or a combination of two or more selected from oxidized dimethyl benzyl tertiary amines, oxidized dimethyl decyl tertiary amines, oxidized dimethyl dodecyl tertiary amines, oxidized dimethyl octyl tertiary amines, and oxidized dimethyl nonyl tertiary amines; and
  • the oxidized hydroxyl-substituted tertiary amines are, for example, one or more selected from oxidized dihydroxymethylbutylamines and oxidized dihydroxyethyldodecyltertiary amines.
  • the catalyst A is selected from oxidized alkyl methyl tertiary amines containing 8-22 carbon atoms, for example, but not limited to, one or a combination of two or more of oxidized dimethyl octyl tertiary amines, oxidized dimethyl nonyl tertiary amines, oxidized dimethyl decyl tertiary amines, and oxidized dimethyl dodecyl tertiary amines.
  • the catalyst A may be involved in the reaction in the form of a solution or in a pure form, and preferably be added in a pure form from the perspective of the reaction.
  • Commercially available oxidized tertiary amines are mostly in the form of aqueous solutions and preferably used after water is removed.
  • the catalyst B is a halide; preferably one or a combination of two or more of an organic bromide, a bromide salt, an iodide salt, and an organic iodide; further preferably one or a combination of two or more of divalent or trivalent metal bromide salts and divalent or trivalent metal iodide salts which are, for example, but not limited to, one or a combination of two or more of calcium bromide, zinc bromide, barium bromide, and cuprous iodide; preferably one or a combination of two or more of calcium salts and barium salts, for example, calcium bromide and/or barium bromide, etc.
  • the mass ratio of the catalyst A to the catalyst B is 0.5-4: 1, preferably 1.5-2.5: 1.
  • a total amount of the catalyst used in step (2) is 0.01% to 3%, preferably 0.1% to 0.5% of the mass of the polyether polyol in step (1).
  • the specific type of the used raw material i.e. polyether polyol is not particularly limited.
  • the polyether polyol used in step (1) has an average molecular weight of 2500-15000, preferably 5000-14000; and an average functionality of at least 2.0, preferably 2.5-6.0.
  • the polyether polyol (also generally referred to as a polyoxyalkylene polyol) is obtained by reacting a starter compound having an active hydrogen atom with one or more epoxy compounds, wherein the epoxy compound(s) is(are), for example, one or more of ethylene oxide, propylene oxide, and butylene oxide.
  • step (1) or step (2) may be performed in the presence or absence of a solvent.
  • the solvent is preferably a proton-free polar solvent and preferably a solvent capable of dissolving an tricarboxylic acid and subsequent epoxy compounds, for example, one or a combination of two or more of acetone, tetrahydrofuran, methyl ethyl ketone, and the like.
  • an polymerization inhibitor may be optionally added (may be or may not be added) in step (2) that is the reaction for preparing the modified polyether.
  • the polymerization inhibitor is, for example, but not limited to, one or a combination of two or more of hydroquinone, p-t-butylcatechol, p-hydroxyanisole, methylhydroquinone, phenothiazine, and diphenylamine.
  • the amount of the polymerization inhibitor is, for example, 0% to 1.5% of the total mass of reductants in step (2), preferably 30-2000 ppm.
  • the compound A in step (1) is preferably maleic anhydride which may be added as a solid or in the form of a solution.
  • the compound A may be in various forms, such as granules, powder, tablets, or the like.
  • the compound A is preferably added in the form of tablets or granules.
  • the molar ratio of maleic anhydride to the polyether polyol is preferably 0.5-1.5: 1, more preferably 0.9-1: 1; and maleic anhydride is reacted with the polyether polyol at a reaction temperature of preferably 80-160 °C, more preferably 120-140 °C.
  • reaction in step (1) may be carried out under normal, negative, or positive pressure, preferably under normal pressure for convenience of operation.
  • the following illustrates a schematic diagram of the reaction for preparing the modified polyether polyol in an embodiment.
  • maleic anhydride is reacted with the polyether polyol, and the resulting product is reacted with the epoxy compound containing a polymerizable double bond (glycidyl methacrylate (GMA)).
  • GMA glycol methacrylate
  • the product i.e. modified polyether polyol obtained in this example has two active sites in series (which are specifically polymerizable unsaturated double bonds in this example).
  • the structure diagram thereof is shown in FIG. 2 . It is to be noted that this is merely an example and should not be construed as limiting the present disclosure.
  • Another aspect of the present disclosure provides a modified polyether polyol, which is prepared by the preparation method described above.
  • the modified polyether polyol provided in another aspect of the present disclosure has the following structural characteristics: the modified polyether polyol includes a polyether segment, an active group A, and an active group B, wherein the active group A is linked to the polyether segment by an ester group, the active group B is linked to the active group A by a linking group which is an organic segment with a molecular weight of less than 200; and the active group A and the active group B are each independently an alkenyl group containing a polymerizable unsaturated double bond, such as a vinyl group, a propenyl group, or the like; preferably, the linking group is one or a combination of two or more selected from an ester group, an ether group, an alkyl group, an amide group, and a thioether group, preferably the linking group contains at least one of a sulfhydryl group and/or a hydroxyl group; further preferably, the linking group contains an ester group and a hydroxyalkyl group, for example, the
  • the modified polyether polyol is prepared by the preparation method described above.
  • the modified polyether polyol prepared in the present disclosure is particularly suitable for being used as a dispersion stabilizer for preparing a copolymer polyol. Therefore, the present disclosure further provides a method for preparing a copolymer polyol, comprising: polymerizing a base polyether polyol with at least one olefinic unsaturated monomer in the presence of an initiator and a dispersion stabilizer to obtain the copolymer polyol; wherein the dispersion stabilizer is the modified polyether polyol described above.
  • the specific type of the base polyether polyol used for preparing the copolymer polyol is not particularly limited and may be determined by those skilled in the art according to the final use of the copolymer polyol.
  • a polyether polyol for general flexible polyurethane foam which is generally a trifunctional base polyether polyol having a hydroxyl value of 54-58 mgKOH/g
  • a polyether polyol for high-resilience foam which is generally a trifunctional base polyether polyol having high activity and a hydroxyl value of 33.5-36.5 mgKOH/g
  • the base polyether polyol in the present disclosure is preferably a trifunctional polyether polyol having a hydroxyl value of 54-58 mgKOH/g.
  • the used olefinic unsaturated monomer is not particularly limited.
  • vinyl monomers suitable for preparing copolymer polyols and accepted in the art may be used, which include, but are not limited to, one or more of aliphatic conjugated dienes, vinyl aromatic compounds, ⁇ , ⁇ -olefinic unsaturated nitriles, ⁇ , ⁇ -olefinic unsaturated nitrile amides, ⁇ , ⁇ -olefinic unsaturated carboxylic acids, ⁇ , ⁇ -olefinic unsaturated carboxylates, vinyl esters, vinyl ethers, vinyl ketones, vinyl halides, and vinylidene halides.
  • the olefinic unsaturated monomer is preferably selected from, but not limited to, a combination of a vinyl aromatic compound and an olefinic unsaturated nitrile, more preferably a combination of styrene and acrylonitrile with a mass ratio of preferably 10: 90 to 90: 10, more preferably 60: 40 to 90: 10.
  • the mass ratio of the olefinic unsaturated monomer to the base polyether polyol is 0.1% to 200%, preferably 30% to 140%.
  • the dispersion stabilizer occupies 0.3% to 10%, preferably 2% to 5% of the total mass of the base polyether polyol and the olefinic unsaturated monomer.
  • the polymerization of the olefinic unsaturated monomer is performed in the presence of the initiator.
  • the amount of the initiator is 0.01 wt% to 5 wt% of the total mass of the base polyether polyol and the olefinic unsaturated monomer.
  • the initiator commonly used in the art may be used, for example, one or a combination of two or more of peroxides and azo compounds.
  • the peroxide is, for example, one or a combination of two or more selected from dibenzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, and di-t-butyl peroxide.
  • the azo compound is, for example, one or a combination of two or more selected from azobisisobutyronitrile (AIBN), azoisovaleronitrile (AMBN), and dimethyl azobisisobutyrate (V601).
  • reaction temperature may be 80-140 °C, preferably 90-120 °C; and the reaction pressure (gauge pressure) may be 0-0.6 Mpa, preferably 0.05-0.4 MPa.
  • the polymerization of the olefinic unsaturated monomer is preferably performed in the presence of a chain-transfer agent.
  • the amount of the chain-transfer agent is preferably 0.1 wt% to 6 wt%, preferably 0.2 wt% to 5 wt% of the total mass of the base polyether polyol and the olefinic unsaturated monomer.
  • the chain-transfer agent is, for example, one or a combination of two or more selected from 1-butanol, 2-butanol, isopropanol, ethanol, methanol, water, cyclohexane, and a thiol.
  • the thiol is, for example, one or a combination of two or more of dodecanethiol, ethanethiol, 1-heptanethiol, 2-octanethiol, and toluenethiol.
  • other compounds may also be used in the process of preparing the copolymer polyol, such as compounds that promote the mixing of components, compounds that reduce viscosity, and/or compounds that can enable one or more of the components used to be better dissolved in a reaction medium.
  • the compounds that reduce the viscosity to promote the mixing of components is, for example, toluene, dichloromethane, or the like.
  • the copolymer polyol may be prepared through batch or continual operations.
  • a specific preparation process of the copolymer polyol may adopt the existing process in the art.
  • the method further includes a process of removing unreacted monomers and the chain-transfer agent, which may be performed by common removal means in the art such as distillation, flash distillation, scraper, thin-film distillation or other chemical unit operations; a heating treatment is generally carried out at a certain degree of vacuum.
  • the copolymer polyol prepared with the modified polyether polyol of the present disclosure is particularly suitable for being used for preparing a polyurethane foam material (such as flexible polyurethane foam). Therefore, the present disclosure further provides a polyurethane foam material, which is obtained through foaming of a composition of the copolymer polyol prepared by the preparation method described above and a polyisocyanate.
  • the polyisocyanate used for preparing the polyurethane foam material may adopt a well-known isocyanate (for example, an isocyanate described in patent document US20034217A1 ) allowed to be used in the field of polyurethane production.
  • the polyisocyanate is preferably one or more of an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, and an aromatic polyisocyanate.
  • the aliphatic polyisocyanate includes, but is not limited to, 1,6-hexamethylene diisocyanate and the like;
  • the cycloaliphatic polyisocyanate includes, but is not limited to, one or a combination of two or more of 1,6-hexamethylene diisocyanate, 1-isocyanate-3,5,5-trimethyl-1,3-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotoluene-diisocyanate, 4,4'-, 2,2'- and 2,4'-bicyclohexyl-methane diisocyanate and isomeric mixtures thereof;
  • the aromatic polyisocyanate includes, but is not limited to, one or a combination of two or more of 2,4- and 2,6-toluene diisocyanate (TDI) and isomeric mixtures thereof, 4,4'-, 2,4'- and 2,2'-diphenylmethane diis
  • the equivalence ratio ((NCO group/active hydrogen atom) ⁇ 100) of NCO groups in the polyisocyanate to active hydrogen atoms in the polyol premix (which refers to other raw material components other than the polyisocyanate), also referred to as an NCO index, may be appropriately adjusted from the perspective of the mechanical properties of polyurethane, for example, preferably 80-140, more preferably 85-120, particularly preferably 95-115.
  • the specific preparation process of polyurethane foam may adopt a corresponding process known in the art.
  • a polyurethane catalyst, a crosslinking agent, a foaming agent, a foam stabilizer, and the like are also commonly added to the reaction system.
  • the polyurethane catalyst may adopt a corresponding catalyst commonly used in the art, and for example, includes, an organometallic compound such as one or a combination of two or more of stannous octoate, stannous oleate, dibutyltin dilaurate, dibutyltin acetate, and dibutyltin diacetate; and an organic amine catalyst such as one or a combination of two or more of bis(2,2'-dimethylamino)ethyl ether, trimethylamine, triethylamine, triethylenediamine, and dimethylethanolamine.
  • the polyurethane catalyst is generally used in an amount of about 0.1% to 3.0% based on the weight of the polyol premix (which refers to other raw material components than the polyisocyanate).
  • An appropriate foaming agent includes one or a combination of two or more of water, acetone, carbon dioxide, halogenated hydrocarbons, aliphatic alkanes, and cycloaliphatic alkanes.
  • the crosslinking agent may adopt a crosslinking agent commonly used in the art and, for example, includes, but is not limited to, glycerol and/or diethanolamine.
  • the crosslinking agent may be used in an amount of less than 3% (w/w), preferably 0.2% to 1.5% (w/w) based on the weight of the polyol premix.
  • appropriate foaming agents include, but are not limited to, one or a combination of two or more of water, acetone, carbon dioxide, halogenated hydrocarbons, aliphatic alkanes, and cycloalkanes.
  • carbon dioxide may be generated through a reaction of water as the foaming agent with the isocyanate and used as the foaming agent.
  • Aliphatic alkanes and cycloalkanes are developed as alternative foaming agents of CFC compounds.
  • the foaming agents may be used alone, or as a mixture of two or more of the foaming agents.
  • the foaming agent is used in an amount of, for example, 0.1% to 20% (w/w) based on the weight of the polyol premix.
  • An appropriate foam stabilizer is, for example, an organopolysiloxane surfactant.
  • the foam stabilizer may be used in an amount of 0.4% to 1% (w/w) based on the weight of the polyol premix.
  • auxiliaries such as flame retardants, fillers, light stabilizers, and antioxidants are also commonly added in an amount of 0.1% to 50% (w/w) based on the weight of the polyol premix, which will not be repeated here one by one.
  • the present disclosure further provides a product containing the polyurethane foam material described above.
  • Polyether polyol A A reaction was carried out using sorbitol as a starter and using KOH as a catalyst in an amount of 0.3% of the mass of propylene oxide (PO) at a reaction temperature of 110 ⁇ 5 °C under a pressure of lower than 0.15 MPa. After PO was fed, the reaction system was aged for 2 h and degassed for 1 h. After degassing, ethylene oxide (EO) was fed, and a reaction was carried out at a reaction temperature of 110 ⁇ 5 °C under a pressure of lower than 0.15 MPa. After materials were fed, the reaction system was aged for 2 h and degassed for 1 h. At this time, the reaction stage ended.
  • PO propylene oxide
  • EO ethylene oxide
  • the reaction product was neutralized by soft water and phosphoric acid added thereto, dehydrated, filtered and cooled to 25 °C for output.
  • the mass ratio of sorbitol, EO, and PO was 1.08: 4.95: 93.97.
  • the polyether polyol A was obtained. After measurement, the polyether polyol had a hydroxyl value of about 28 mgKOH/g, an average molecular weight of 11400 g/mol, and an average functionality of 5.7.
  • Base polyol B a polyether polyol for high-resilience and flexible foam, prepared by reacting glycerol with propylene oxide and ethylene oxide, available from Wanhua Chemical Group Co., Ltd., WANOL®F3135.
  • Base polyether polyol a polyether polyol for ordinary flexible foam, prepared by reacting glycerol with propylene oxide and ethylene oxide, available from Wanhua Chemical Group Co., Ltd., WANOL®F3136.
  • OA-12 an oxidized dimethyl dodecyl tertiary amine, which is dehydrated and dried to obtain a viscous liquid.
  • WANNATE®8001 modified diphenylmethane diisocyanate (MDI) from Wanhua Chemical Group Co., Ltd.
  • BiCAT®8106 an organic bismuth catalyst from Shepherd Chemical Company.
  • B-8715 LF2 a foam stabilizer from TMG Chemicals Co., Ltd.
  • dispersion stabilizer 1 3000 g of polyether polyol A, 24.2g of maleic anhydride, and 3 g of KOH were mixed uniformly, heated to 120 °C, and reacted for 5 h.
  • dispersion stabilizer 2 3000 g of polyether polyol A, 22.5g of itaconic anhydride, and 3 g of KOH were mixed uniformly, heated to 130 °C, and reacted for 3 h.
  • copolymer polyol 1 A 500 mL four-necked bottle equipped with a stirrer, a heating device, a temperature control device, and a feeder was used as a reactor. 55.4 g of base polyol B and 5.6 g of dispersion stabilizer 1 were added to the reactor.
  • top materials a mixed solution of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL®F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile
  • top materials a mixed solution of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL®F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile
  • reaction system was aged for 1 h and heated to 160 °C.
  • the unreacted monomers were removed under vacuum for 2 h to obtain a product.
  • the indexes of the product were measured.
  • the solid content was 44.6% and the viscosity was 4950 cp (25 °C).
  • copolymer polyol 2 A 500 mL four-necked bottle equipped with a stirrer, a heating device, a temperature control device, and a feeder was used as a reactor. 55.4 g of base polyol B and 5.6 g of dispersion stabilizer 2 were added to the reactor.
  • top materials a mixed solution of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL®F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile
  • top materials a mixed solution of 10.47 g of isopropanol, 85.71 g of base polyether polyol WANOL®F3156, 46.55 g of acrylonitrile, 69.83 g of styrene, and 1.21 g of azobisisobutyronitrile
  • reaction system was aged for 1 h and heated to 160 °C.
  • the unreacted monomers were removed under vacuum for 2 h to obtain a product with a solid content of 44.5% and a viscosity of 5018 cp (25 °C).
  • dispersion stabilizer 3 3000 g of polyether polyol A and 30.6 g of maleic anhydride were heated to 120 °C and reacted for 12 h under nitrogen protection. Then, 50 g of ethylene oxide (EO) were added and the reaction was continued for 4 h at 130 °C. Unreacted EO was removed to obtain a product as a transparent brown-yellow liquid with a viscosity of 5500 mPa.s and a measured unsaturation of 0.045 meq/g.
  • the modified polyether polyols prepared in Examples 1 and 2 had higher unsaturation and more active sites than this comparative example.
  • a 500 mL four-necked bottle equipped with a stirrer, a heating device, a temperature control device, and a feeder was used as a reactor. 55.4 g of base polyol B and 5.6 g of comparative dispersion stabilizer 3 were added to the reactor.
  • Method for preparing polyurethane foam Premixes were prepared according to raw materials and their parts by weight in Table 1. The premixes and an isocyanate were placed at a constant temperature of 22 °C for 3 h, separately. Then, 100 g of each premix and 60 g of isocyanate WANNATE®8001 were stirred to be mixed in a stirrer (with rotational speed of 3000 rpm) for 6s. The stirred mixture was quickly poured into an aluminum open mold (size: 300 mm length, 300 mm width, and 50 mm thickness) previously heated to 60 °C so that the mixture was allowed to foam. After 7 min, the foam was taken out to obtain the polyurethane foam.
  • polyurethane foams 1#, 2#, and 3# were prepared using the copolymer polyols prepared in Comparative Example, Example 3, and Example 4, respectively.
  • foam microstructures of polyurethane foams 1#, 2#, and 3# were observed using an Olympus IX73 microscope. The results are shown in FIGS. 3 to 5 , respectively.
  • Foam 1# had many large and coarse pores, with pores being messy; foams 2# and 3# had few coarse pores, with pores being fine.
  • the copolymer polyols prepared with the modified polyether polyols of the present disclosure in the embodiments of the present disclosure had lower viscosity and good filterability; and the polyurethane foam prepared with the obtained copolymer polyols had better comprehensive performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP18944686.7A 2018-12-26 2018-12-26 Polyol de polyéther modifié et son utilisation dans des matériaux en mousse de polyuréthane Pending EP3904421A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/123901 WO2020132944A1 (fr) 2018-12-26 2018-12-26 Polyol de polyéther modifié et son utilisation dans des matériaux en mousse de polyuréthane

Publications (2)

Publication Number Publication Date
EP3904421A1 true EP3904421A1 (fr) 2021-11-03
EP3904421A4 EP3904421A4 (fr) 2022-07-13

Family

ID=71126118

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18944686.7A Pending EP3904421A4 (fr) 2018-12-26 2018-12-26 Polyol de polyéther modifié et son utilisation dans des matériaux en mousse de polyuréthane

Country Status (3)

Country Link
US (1) US11780954B2 (fr)
EP (1) EP3904421A4 (fr)
WO (1) WO2020132944A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3904416B1 (fr) * 2018-12-26 2023-04-19 Wanhua Chemical Group Co., Ltd. Stabilisateur macromonomère, son procédé de préparation et procédé de préparation de polyol polymère
US11866543B2 (en) * 2021-05-06 2024-01-09 Covestro Llc Glycidyl (meth)acrylate polymer polyol stabilizers

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5328936B2 (fr) * 1971-12-03 1978-08-17
US3960935A (en) 1972-06-22 1976-06-01 The Kendall Company Nonionic monomeric emulsion stabilizers
US4390645A (en) 1979-11-23 1983-06-28 The Dow Chemical Company Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom
US4550194A (en) 1982-04-01 1985-10-29 Basf Wyandotte Corporation Process for the preparation of polyether-ester polyols
JPS59161406A (ja) 1983-03-04 1984-09-12 Dai Ichi Kogyo Seiyaku Co Ltd 安定な共重合体エマルジヨンの製造法
IT1186117B (it) 1985-11-29 1987-11-18 Snia Fibre Struttura di magazzino per bobine di filato
US5268418A (en) * 1990-06-12 1993-12-07 Arco Chemical Technology, L.P. Polymer/polyol and preformed stabilizer systems
US5364906A (en) 1993-08-20 1994-11-15 Arco Chemical Technology, L.P. Low viscosity polymer polyols with improved dispersion stability
ZA99973B (en) 1998-02-09 1999-08-10 Shell Int Research Macromer stabiliser precursor for polymer polyols.
US6624209B2 (en) 1999-07-30 2003-09-23 Sanyo Chemical Industries, Ltd. Polymer polyol composition, process for producing the same, and process for producing polyurethane resin
US6994839B2 (en) 2001-08-15 2006-02-07 Ovonic Battery Company, Inc. Carbonate recycling in a hydrogen producing reaction
US7160975B2 (en) 2004-08-02 2007-01-09 Bayer Materialscience Llc Methacrylates as stabilizers for polymer polyols
KR100839061B1 (ko) 2006-12-15 2008-06-19 금호석유화학 주식회사 무수말레인산을 이용한 폴리머 폴리올을 위한 제조용 안정제
US20080262119A1 (en) 2007-04-04 2008-10-23 Jeroen Patrick Michel Bouwman Process for preparing polymer polyols
WO2012017016A1 (fr) 2010-08-03 2012-02-09 Shell Internationale Research Maatschappij B.V. Procédé de préparation de polyols polymériques
US10040903B2 (en) 2016-09-13 2018-08-07 Covestro Llc Polymer polyol quality
CN108623757A (zh) 2018-06-07 2018-10-09 山东隆华新材料股份有限公司 聚合物多元醇的制备方法
EP3904416B1 (fr) * 2018-12-26 2023-04-19 Wanhua Chemical Group Co., Ltd. Stabilisateur macromonomère, son procédé de préparation et procédé de préparation de polyol polymère
US11866543B2 (en) * 2021-05-06 2024-01-09 Covestro Llc Glycidyl (meth)acrylate polymer polyol stabilizers

Also Published As

Publication number Publication date
EP3904421A4 (fr) 2022-07-13
US20210355263A1 (en) 2021-11-18
BR112021008689A2 (pt) 2021-08-10
US11780954B2 (en) 2023-10-10
WO2020132944A1 (fr) 2020-07-02

Similar Documents

Publication Publication Date Title
KR101699073B1 (ko) 천연 오일 베이스 폴리올을 포함하는 중합체 폴리올, 이들 중합체 폴리올을 포함하는 폴리우레탄 발포체 및 이들의 제조 방법
JP5082847B2 (ja) 軟質ポリウレタンフォームおよびその製造方法、該軟質ポリウレタンフォームを用いた自動車用シート
JP5145935B2 (ja) 軟質ポリウレタンフォームおよびその製造方法、該軟質ポリウレタンフォームを用いた自動車用シート
US5554662A (en) Low viscosity polymer polyols a process for their production as well as the manufacture of polyurethane from materials
US7960496B2 (en) Method for preparing polymer polyol stabilizer using maleic anhydride, and polymer polyol stabilizer prepared thereby
CA2187125A1 (fr) Procede continu de fabrication de polyols polymeriques a faible viscosite faits de particules tres stables de taille moyenne petite
EP3568425B1 (fr) Polyols polymères comprenant des polyols de polyéther à base d'amine et procédé de préparation de ces polyols polymères
EP2894180A1 (fr) Polyols polymères comprenant un polyol de polyéthercarbonate comme polyol de base
US11780954B2 (en) Modified polyether polyol and use thereof in polyurethane foam materials
KR20150126925A (ko) 폴리부타디엔 개질된 중합체 폴리올, 폴리부타디엔 개질된 중합체 폴리올로부터 제조된 발포체, 및 그의 제조 방법
JP3083235B2 (ja) ポリマーポリオール、その製造方法および軟質高弾性ポリウレタンフォームの製造方法
CN109705305B (zh) 含有多不饱和基团异氰酸酯缩二脲及其制备和应用
CN109796588B (zh) 改性聚醚多元醇及其在聚氨酯泡沫材料中的应用
US11945775B2 (en) Stable dispersant and application thereof in preparing copolymer polyols
JPH0559134A (ja) 重合体ポリオール組成物の製法およびポリウレタン樹脂の製法
KR20060040034A (ko) 폴리머 폴리올 제조용 분산 안정제
BR112021008689B1 (pt) Método para a preparação de um poliol poliéter modificado, poliol poliéter modificado, método para preparar um copolímero poliol, material de espuma de poliuretano e produto
JPH01161007A (ja) ポリマーポリオールおよびポリウレタンの製造法
CN109734896B (zh) 一种“Gemini”型稳定分散剂及其合成和应用
JP2821572B2 (ja) 重合体ポリオール組成物および撥水性ポリウレタンの製造方法
DE19702208A1 (de) Niedrigviskose Polymerpolyole, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung zur Herstellung von Polyurethanschaumstoffen
EP1370597A1 (fr) Procede d'obtention de mousses flexibles de polyurethanne
JPH01161008A (ja) ポリマーポリオール及びポリウレタンの製造方法
JP2995282B2 (ja) 重合体ポリオール組成物および撥水性ポリウレタンの製造方法
JPS595608B2 (ja) ポリマ−ポリオ−ルの製造方法

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210416

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

A4 Supplementary search report drawn up and despatched

Effective date: 20220615

RIC1 Information provided on ipc code assigned before grant

Ipc: C08G 18/76 20060101ALI20220610BHEP

Ipc: C08G 18/22 20060101ALI20220610BHEP

Ipc: C08G 18/18 20060101ALI20220610BHEP

Ipc: C08G 18/16 20060101ALI20220610BHEP

Ipc: C08F 290/06 20060101ALI20220610BHEP

Ipc: C08F 212/08 20060101ALI20220610BHEP

Ipc: C08F 220/44 20060101ALI20220610BHEP

Ipc: C08F 283/06 20060101ALI20220610BHEP

Ipc: C08G 18/32 20060101ALI20220610BHEP

Ipc: C08G 18/48 20060101ALI20220610BHEP

Ipc: C08G 18/63 20060101ALI20220610BHEP

Ipc: C08G 18/65 20060101ALI20220610BHEP

Ipc: C08G 18/66 20060101ALI20220610BHEP

Ipc: C08G 65/332 20060101AFI20220610BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20240423